Diesel exhaust gas purification catalyst and diesel exhaust gas purification system

ABSTRACT

A diesel exhaust gas purification catalyst contains a substrate, and a catalyst layer formed on the substrate. The catalyst layer contains a carrier, a noble metal and/or an oxide thereof supported by the carrier, and a composite oxide of cerium and one or more Group III and/or Group IV elements. The diesel exhaust gas purification catalyst when in use is disposed on an upstream side of an exhaust gas stream with respect to a denitration catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 13/101,901, filed May5, 2011, now allowed, which is a continuation of PCT InternationalApplication No. PCT/JP2009/069008, filed Nov. 6, 2009, which claimspriority of Japanese Patent Application No. 2008-285544, filed Nov. 6,2008, the contents of each of which are hereby incorporated by referencein their entirety into this application.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a technique for exhaust gaspurification.

2. Description of the Related Art

In recent years, exhaust gas regulations for automobiles and the likehave been enforced. To cope with these regulations, various exhaust gaspurification catalysts which are configured to efficiently removehydrocarbons (HC), carbon monoxides (CO), nitrogen oxides (NO_(x)) andthe like in exhaust gas have been developed (see, for example,Non-patent Document 1).

However, conventional exhaust gas purification catalysts may not achievesufficient purification performance for exhaust gas such as NO_(x).

PRIOR ART DOCUMENTS Non-Patent Documents

Non-patent Document 1: “Catalyst Utilization Dictionary”, EditorialBoard of Catalyst Utilization Dictionary ed., Kogyo Chosakai PublishingCo., Ltd. (2004), PP. 794-799

BRIEF SUMMARY OF THE INVENTION

An object of the present invention is to achieve excellent exhaust gaspurification performance, and especially to achieve excellent NO_(x)purification performance.

According to a first aspect of the present invention, there is provideda diesel exhaust gas purification catalyst, comprising: a substrate; anda catalyst layer formed on the substrate, the catalyst layer comprisinga carrier, a noble metal and/or an oxide thereof supported by thecarrier, and a composite oxide of cerium and one or more Group IIIand/or Group IV elements, wherein the catalyst when in use is disposedon an upstream side of an exhaust gas stream with respect to adenitration catalyst.

According to a second aspect of the present invention, there is provideda diesel exhaust gas purification system, comprising: the diesel exhaustgas purification catalyst according to the first aspect; and adenitration catalyst to which exhaust gas that has passed through thediesel exhaust gas purification catalyst is fed.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIG. 1 is a cross-sectional view schematically showing the dieselexhaust gas purification catalyst according to an embodiment of thepresent invention.

FIG. 2 is a schematic view showing an example of the diesel exhaust gaspurification system using the diesel exhaust gas purification catalystshown in FIG. 1.

FIG. 3 is a cross-sectional view schematically showing a variation ofthe diesel exhaust gas purification catalyst shown in FIG. 1.

FIG. 4 is a cross-sectional view schematically showing another variationof the diesel exhaust gas purification catalyst shown in FIG. 1.

FIG. 5 is a schematic drawing showing a variation of the diesel exhaustgas purification system shown in FIG. 2.

FIG. 6 is a schematic view showing another variation of the dieselexhaust gas purification system shown in FIG. 2.

FIG. 7 is a graph showing the results of the measurements of the NO_(x)adsorption amounts of the diesel exhaust gas purification catalysts.

FIG. 8 is a graph showing the measurement result of the HC and COconversion of the diesel exhaust gas purification catalysts.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have made intensive studies aiming at solving the problemsmentioned above. During the process therefor, the inventors have foundthat a denitration catalyst for purifying NO_(x) may not achievesufficient NO_(x) purification performance at a temperature lower than acertain temperature (hereinafter referred to as an activationtemperature; for example, about 200° C.). Namely, the inventors havefound that when a diesel engine in which the temperature of exhaustedgas emitted therefrom is relatively low is used, a denitration catalystis not likely to achieve sufficient NO_(x) purification performance.Therefore, the present inventors have developed a diesel exhaust gaspurification catalyst focusing on the following points. As a result, thepresent inventors have obtained an idea of disposing a catalystcomprising a composite oxide of cerium and one or more Group III and/orGroup IV elements on the upstream side of an exhaust gas stream withrespect to a denitration catalyst.

Cerium has a property that its ion valency is readily varied as comparedto other elements. Therefore, the valency tends to be varied betweenCe³⁺ and Ce⁴⁺, for example, in cerium oxide. Therefore, cerium oxidecauses the following reactions in accordance with the variation of theconcentration of surrounding oxygen.2CeO₂→Ce₂O₃+½O₂  (1)Ce₂O₃+½O₂→2CeO₂  (2)

Namely, when the concentration of surrounding oxygen is low, oxygen isreleased by the reaction of (1). On the other hand, when theconcentration of surrounding oxygen is high, oxygen is absorbed by thereaction of (2). Thus, cerium oxide has a performance of adjusting theconcentration of surrounding oxygen by releasing and absorbing oxygenreversibly. This performance is generally referred to as oxygen storagecapacity.

Cerium oxide has a crystal structure in which atoms are packed densely.Therefore, it is considered that diffusion of oxygen in the crystal ishard to occur. Therefore, the storage and release of oxygen is expectedto occur only around the surface of cerium oxide.

Therefore, a composite oxide of cerium oxide and other metal oxide hasbeen conventionally used as an oxygen storage material. In suchcomposite oxide, relatively large gaps are formed in the crystal due tothe different sizes of the atoms of cerium and other metal elements.Therefore, it is considered that diffusion of oxygen in the crystaloccurs more easily as compared to cerium oxide. Accordingly, it isexpected that not only the vicinity of the surface of the crystal butalso the inside of the crystal contribute to the storage and release ofoxygen.

In the present embodiment, as mentioned above, a composite oxide ofcerium and one or more Group III and/or Group IV elements is used. It isconsidered that the Group III and/or Group IV elements are stronglybound to oxygen. Furthermore, it is expected that the Group III and/orGroup IV elements cause less valency variation as compared to cerium.Therefore, in a low temperature region where heat energy is small (forexample, a temperature region whose temperature being lower than theactivation temperature), it is expected that the reaction for releasingoxygen that corresponds to the (1) is relatively hard to occur. Namely,it is considered that oxygen is readily retained in the crystal at a lowtemperature region in the composite oxide used in the presentembodiment.

At least a part of the elements bound to the stored oxygen has a 4forbital and/or a 5d orbital having high electron-acceptability. Namely,at least a part of these elements has a 4f orbit and/or a 5d orbitalthat is not occupied by electrons or is occupied only by an unpairedelectron. Furthermore, it is considered that the orbital occupied by theelectrons possessed by NO_(x) can form a bonding molecular orbitalbetween these orbitals. Therefore, in this case, the element may act asan adsorbing site for adsorbing NO_(x). Namely, it is considered thatthis composite oxide may act as a NO_(x) storage material at a lowtemperature region.

On the other hand, it is considered that the stored oxygen is releasedfrom the composite oxide at a high temperature region at which heatenergy is high (for example, a temperature region whose temperaturebeing the activation temperature or higher). Therefore, it is expectedthat the valency of the elements that are bound to the oxygen isdecreased and the electron-acceptability thereof is also decreased.Namely, it is expected that the binding between these elements andNO_(x) becomes relatively weak. Furthermore, at the high temperatureregion, the heat oscillation of the adsorbed NO_(x) also becomes active.Therefore, it is considered that this composite oxide releases not onlythe stored oxygen but also the adsorbed NO_(x) at the high temperatureregion.

As mentioned above, it is expected that the composite oxide of thepresent embodiment has a function to adsorb NO_(x) at a low temperatureregion (for example, a temperature region whose temperature being lowerthan the activation temperature) and to release NO_(x) at a hightemperature region (for example a temperature region whose temperaturebeing the activation temperature or higher). Therefore, the presentinventors conceived that the problems of the denitration catalyst can beeliminated by disposing a catalyst comprising this composite oxide onthe upstream side of an exhaust gas stream with respect to thedenitration catalyst.

Namely, when the temperature of exhaust gas is low, the NO_(x) in theexhaust gas is adsorbed on the catalyst disposed on the upstream side.Then, when the temperature of the exhaust gas is raised, the NO_(x)adsorbed on the catalyst disposed on the upstream side is released andflown into the denitration catalyst disposed on the downstream side.Namely, the exhaust gas at a relatively high temperature, for example,at a temperature being the activation temperature or higher is mainlyflown into the denitration catalyst. Therefore, the denitration catalystcan exhibit excellent NO_(x) purification performance at a broadertemperature range as compared to conventional ones.

Hereinafter, the embodiments of the present invention are explained withreference to drawings. Throughout the drawings, the same referencenumerals are used for constitutional elements that exhibit the same orsimilar function, and redundant explanations have been omitted.Furthermore, as used herein, the “composite oxide” means that aplurality of oxides form a solid solution rather than a mere physicalmixture of oxides.

FIG. 1 is a cross-sectional view schematically showing the dieselexhaust gas purification catalyst according to an embodiment of thepresent invention. FIG. 2 is a schematic view showing an example of thediesel exhaust gas purification system using the diesel exhaust gaspurification catalyst shown in FIG. 1.

The diesel exhaust gas purification catalyst shown in FIG. 1 comprisessubstrate 10 and catalyst layer 20 formed on the substrate 10. Thecatalyst 1 is used by disposing on the upstream side of an exhaust gasstream with respect to denitration catalyst 2, shown in FIG. 2. Namely,the diesel exhaust gas purification system S1 shown in FIG. 2 comprisesthe catalyst 1 and the denitration catalyst 2 to which the exhaust gasthat has passed through the catalyst 1 is supplied.

As the substrate 10, for example, a monolithic-honeycomb type substrateis used. Typically, the substrate 10 is made of a ceramic such ascordierite.

The catalyst layer 20 comprises a carrier, a noble metal and/or an oxidethereof supported by the carrier, and a composite oxide of cerium andone or more Group III and/or Group IV elements.

The carrier plays roles to increase the specific surface area of thenoble metal and/or an oxide thereof, and to dissipate the heatgeneration due to the reaction to suppress the sintering of the noblemetal and/or an oxide thereof. The carrier comprises, for example, atleast one element selected from aluminum (Al), titanium (Ti), zirconium(Zr) and silicon (Si). Typically, oxides such as alumina, titania,zirconia and silica are used as the carrier.

The noble metal and/or an oxide thereof plays a role to catalyze areaction for purifying exhaust gas, especially the oxidation reactionbetween HC and CO. As the noble metal, for example, platinum groupelements such as platinum (Pt), palladium (Pd) and rhodium (Rh) areused. A plurality of kinds of elements may also be used as the noblemetal.

As mentioned above, the composite oxide of cerium and one or more GroupIII and/or Group IV elements plays a role to adsorb NO_(x) in theexhaust gas at a low temperature region and release NO_(x) at a hightemperature region. As is previously mentioned, the denitration catalyst2 disposed on the downstream side of the catalyst 1 cannot exhibitexcellent NO_(x) purification performance at a temperature region lowerthan the activation temperature (for example, 200° C.). On the otherhand, when the catalyst 1 comprising the composite oxide is disposed onthe upstream side, the NO_(x) in the exhaust gas can be retained in thecatalyst 1 until the temperature of the exhaust gas becomes sufficientlyhigh. Therefore, it is possible to improve the apparent NO_(x)purification performance of the denitration catalyst 2.

As the Group III element included in the composite oxide other thancerium, for example, yttrium (Y), a lanthanoid and/or an actinoid isused. As the lanthanoid, for example, lanthanum (La), praseodymium (Pr)and/or neodymium (Nd) is used. As the Group IV element, for example,titanium (Ti) and/or zirconium (Zr) is used. The composite oxide mayfurther include barium (Ba) and/or aluminum (Al).

The composite oxide is typically a composite oxide of cerium and one ormore lanthanoid and/or actinoid other than cerium. For example, thecomposite oxide is a composite oxide of cerium and praseodymium, or acomposite oxide of cerium, lanthanum and praseodymium. The ratio ofcerium in the composite oxide is, for example, in the range of from 55%by mass to 95% by mass in terms of oxide, and typically in the range offrom 70% by mass to 90% by mass in terms of oxide. The temperature atwhich release of NO_(x) occurs can suitably be adjusted by varying theratio. Namely, by changing this ratio, NO_(x) can be released from thecatalyst 1 at a temperature that conforms to the activation temperatureof the denitration catalyst 2 that is used in combination with thecatalyst 1.

The composite oxide has a specific surface area of, for example, 150m²/g or more. The composite oxide has a specific surface area of, forexample, 180 m²/g or more, typically 200 m²/g or more. Namely, thecomposite oxide has a relatively high specific surface area. Therefore,it has a large contact surface area with NO_(x) in exhaust gas, and theadsorption thereof readily occurs.

The “specific surface area” can be obtained from an N₂ adsorptionisotherm measured at 77.4 K. Specifically, at first, the amount ofnitrogen gas adsorbed on active carbon (mL/mL) is measured for everypressure P (mmHg) of nitrogen gas of 77.4 K (boiling point of nitrogen)while gradually increasing the pressure P in the nitrogen gas. Then,relative pressure P/P₀ is obtained as a value obtained by dividing thepressure P (mmHg) by the saturated vapor pressure P/P₀ (mmHg) of thenitrogen gas, and the amount of adsorbed nitrogen gas against respectiverelative pressure P/P₀ is plotted to give an adsorption isotherm. Then,a BET plot is prepared based on this adsorption isotherm, and a BETspecific surface area is determined. Thus, the above “specific surfacearea” is obtained.

The composite oxide may be supported by the carrier together with thenoble metal and/or an oxide thereof. By doing so, the apparent specificsurface area of the composite oxide can be improved. Namely, the NO_(x)adsorption performance of the composite oxide can further be improved.

The mass ratio of the composite oxide in the catalyst layer 20 isadjusted to, for example, from 10% by mass to 85% by mass. When theamount is small, excellent NO_(x) adsorption performance may sometimesnot be achieved. When the amount is high, excellent HC and COpurification performance may sometimes not be achieved.

The catalyst layer 20 may further comprise zeolite. Zeolite has a highspecific surface area and excellent adsorption performance for HC inexhaust gas. Therefore, the HC purification performance of the catalyst1 can further be improved by incorporating zeolite. As the zeolite, forexample, type-β zeolite (β zeolite), mordenite, ZSM-5, or a mixturethereof is used. The ratio of zeolite in the catalyst layer 20 isadjusted to, for example, the range of from 40% by mass to 80% by mass,typically the range of from 50% by mass to 80% by mass.

The catalyst layer 20 may further comprise a binder. The binder plays arole to improve the durability of the catalyst 1 by strengthen thebinding among the carrier particles and the binding between the carrierparticles and the noble metal and/or an oxide thereof. As the binder,for example, an alumina sol, a titania sol or a silica sol is used.

The catalyst layer 20 may be of a monolayer structure or of a multilayerstructure.

FIG. 3 is a cross-sectional view schematically showing a variation ofthe diesel exhaust gas purification catalyst shown in FIG. 1. The dieselexhaust gas purification catalyst 1 shown in FIG. 3 has the sameconstitution as the diesel exhaust gas purification catalyst shown inFIG. 1, except that the catalyst layer 20 comprises a first catalystlayer 20A formed on the substrate 10 and a second catalyst layer 20Bformed on the first catalyst layer 20A.

In these catalyst layers 20A and 20B, the kinds, contents per unitsurface area, etc. of the component such as the carrier, the noble metaland/or an oxide thereof, the composite oxide, zeolite and the binderdiffer from each other. By doing so, the NO_(x) adsorption performance,exhaust gas purification performance of the catalyst 1, and the apparentexhaust gas purification performance of the catalyst 2 that is disposedon the downstream side of the catalyst 1 can be optimized.

The first catalyst layer 20A and the second catalyst layer 20B differfrom each other in, for example, the composite oxide content in thesubstrate per unit volume (hereinafter also referred to as compositeoxide content). When the NO_(x) purification performance of the catalyst1 is important, the following constitution is typically adopted. Namely,the second catalyst layer 20B includes a larger content of the compositeoxide per unit volume of the substrate as compared to that in the firstcatalyst layer 20A. In this case, the first catalyst layer 20A does nothave to include the composite oxide.

When the second catalyst layer 20B has a larger composite oxide contentas compared to that of the first catalyst layer 20A, each layer mainlyplays the following role. Namely, the second catalyst layer 20B mainlycontributes to adsorption and purification of NO_(x). Furthermore, thefirst catalyst layer 20A mainly contributes to purification of CO andHC.

When the composite oxide content in the second catalyst layer 20B islarger than that of the first catalyst layer 20A, the followingadvantages become available. Namely, the second catalyst layer 20Bcontacts with NO_(x) molecules in the exhaust gas more readily than thefirst catalyst layer 20A does. Furthermore, since the composite oxide ispresent in a relatively large amount in the second catalyst layer 20B,the composite oxide readily contacts with NO_(x) molecules. Therefore,in this case, the NO_(x) purification performance of the catalyst isimproved. Furthermore, a CO molecule is relatively small in size.Therefore, it is considered that many of the CO molecules in the exhaustgas pass through the second catalyst layer 20B and react in the firstcatalyst layer 20A. Therefore, even in the case when the constitution asmentioned above is adopted, excellent CO purification performance can bemaintained.

When the NO_(x) purification performance of the catalyst 1 is important,the ratio of the composite oxide content in the second catalyst layer20B with respect to the composite oxide content in the first catalystlayer 20A is adjusted to, for example, in the range of from 1.5 to 9.0,typically in the range of from 1.5 to 4.0.

FIG. 4 is a cross-sectional view schematically showing another variationof the diesel exhaust gas purification catalyst shown in FIG. 1.

The catalyst 1 comprises a first part P1 to which exhaust gas is fed,and a second part P2 to which the exhaust gas that has passed throughthe first part P1 is fed. Namely, the first part P1 is positioned on theupstream side of the exhaust gas stream, and the second part P2 ispositioned on the downstream side of the exhaust gas stream. Thecatalyst 1 is also used by disposing on the upstream side of the exhaustgas stream with respect to the denitration catalyst 2 shown in FIG. 2.

In this example, the first part P1 and the second part P2 are differentfrom each other in the composite oxide content per unit volume.Typically, the first part P1 has a lower content of the composite oxideper unit volume as compared to that of the second part P2. In this case,the first part P1 does not have to include the composite oxide.

When the adsorption site of the composite oxide is covered by aparticular material (PM) and the like emitted from a diesel engine, theNO_(x) adsorption performance of the composite oxide is decreased. Thisphenomenon is particularly significant in the first part P1 positionedon the upstream side of the exhaust gas stream. Furthermore, the firstpart P1 has a higher heat load than that of the second part P2.Therefore, it is advantageous that the composite oxide is included in alarger content in the second part P2 positioned on the downstream sideof the exhaust gas stream.

Furthermore, by purifying PM in the first part P1 of the catalyst 1 tosome extent, it is possible to make a decrease in the NO_(x) adsorptionperformance due to adsorption of PM, clogging by PM, and the likedifficult to occur in the second part P2 that has a larger content ofthe composite oxide per unit volume. Furthermore, by doing so, theexhaust gas in which large amounts of CO and HC have been purified inthe first part P1 is flown into the second part P2. Therefore, byadopting such a constitution, the apparent NO_(x) adsorption performanceof the denitration catalyst 2 can further be improved.

The ratio of the composite oxide content in the second part P2 relativeto the composite oxide content in the first part P1 is, for example,within the range from 1.5 to 9.0, typically within the range from 4.0 to9.0.

FIG. 5 is a schematic drawing showing a variation of the diesel exhaustgas purification system shown in FIG. 2. FIG. 6 is a schematic viewshowing another variation of the diesel exhaust gas purification systemshown in FIG. 2.

The system S2 shown in FIG. 5 comprises a diesel oxide catalyst 100, thediesel exhaust gas purification catalyst 1 to which the exhaust gas thathas passed through the catalyst 100 is supplied, and a denitrationcatalyst 300 to which the exhaust gas that has passed through the dieselexhaust gas purification catalyst 1 is supplied. Namely, in this systemS2, the diesel exhaust gas purification catalyst 1 is disposed betweenthe diesel oxidizing catalyst 100 and the denitration catalyst 300.

Since the diesel exhaust gas purification catalyst 1 comprises the abovecomposite oxide, it can adsorb NO_(x) in the exhaust gas at atemperature region whose temperature being lower than the activationtemperature of the denitration catalyst 300, the activation temperaturebeing, for example, 200° C. Therefore, the NO_(x) in the exhaust gas canbe retained in the diesel exhaust gas purification catalyst 1 until thetemperature of the exhaust gas is sufficiently raised. Therefore, byadopting such constitution, the apparent NO_(x) purification performanceof the denitration catalyst 300 can be improved.

Furthermore, as mentioned above, the exhaust gas that has passed throughthe diesel oxidizing catalyst 100 is supplied to the diesel exhaust gaspurification catalyst 1. In this case, the exhaust gas in which PM hasbeen at least partially removed by the diesel oxidizing catalyst 100 issupplied to the diesel exhaust gas purification catalyst 1. Therefore, adecrease in the NO_(x) adsorption performance of the diesel exhaust gaspurification catalyst 1 due to adsorption of PM, clogging by PM, and thelike is difficult to occur. Namely, the apparent NO_(x) adsorptionperformance of the denitration catalyst 300 can be improved.

The system S3 shown in FIG. 6 further comprises a diesel particulatefilter (DPF) 400. The DPF plays a role to purify the PM emitted from thediesel engine. As the DPF, for example, a wall-flow type honeycomb isused.

In the system S3, the DPF 400 is disposed between the diesel oxidizingcatalyst 100 and the diesel exhaust gas purification catalyst 1. In thesystem S3, the exhaust gas passes the DPF 400 before it is supplied tothe diesel exhaust gas purification catalyst 1. Therefore, the PMemitted from the diesel engine is purified not only by the dieseloxidizing catalyst 100 but by the DPF 400. Therefore, a decrease in theNO_(x) adsorption performance of the diesel exhaust gas purificationcatalyst 1 due to adsorption of PM and the like is further difficult tooccur. Namely, the apparent NO_(x) adsorbing performance of thedenitration catalyst 300 is further improved.

In addition, the diesel exhaust gas purification system may comprise thediesel exhaust gas purification catalyst 1, the diesel oxidizingcatalyst 100 to which the exhaust gas that has passed through the dieselexhaust gas purification catalyst 1 is supplied, and the denitrationcatalyst 300 to which the exhaust gas that has passed through the dieseloxidizing catalyst 100 is supplied. Furthermore, the system may furthercomprise a DPF between the diesel oxidizing catalyst 100 and thedenitration catalyst 300.

EXAMPLES Example 1 Preparation of Catalyst C1

100 g of alumina, 100 g of pure water, and a platinum nitrate solutioncontaining 4 g of platinum were mixed. This was dried at 250° C., andcalcined at 500° C. for 3 hours in air. A catalyst powder was thusobtained. Hereinafter, this is referred to as “catalyst powder A”.

A composite oxide of cerium and praseodymium was prepared. The ratio ofcerium in this composite oxide was adjusted to 90% by mass in terms ofoxide. The specific surface area of the obtained composite oxide was 150m²/g. Hereinafter, this composite oxide is referred to as “compositeoxide A”.

100 g of the catalyst powder A, 50 g of the composite oxide A, 50 g ofan alumina sol and 100 g of pure water were mixed to prepare a slurry.Hereinafter, this slurry is referred to as “slurry A”.

A monolithic honeycomb carrier having a volume of 0.035 L was coatedwith the slurry A. This was dried at 250° C. for 1 hour, and calcined at500° C. for 1 hour. A diesel exhaust gas purification catalyst was thusprepared. Hereinafter, this catalyst is referred to as “catalyst C1”.

Example 2 Preparation of Catalyst C2

First, 100 g of alumina, 50 g of the composite oxide A, 50 g of analumina sol, 100 g of pure water, and a platinum nitrate solutioncontaining 4 g of platinum were mixed to prepare a slurry. Hereinafter,this slurry is referred to as “slurry B”.

Then, a diesel exhaust gas purification catalyst was prepared in asimilar manner to that explained for the catalyst C1, except that theslurry B was used instead of the slurry A. Hereinafter, this catalyst isreferred to as “catalyst C2”.

Example 3 Preparation of Catalyst C3 (Comparative Example)

First, 100 g of the catalyst powder A, 50 g of an alumina sol, and 100 gof pure water were mixed to prepare a slurry. Hereinafter, this slurryis referred to as “slurry C”.

Then, a diesel exhaust gas purification catalyst was prepared in asimilar manner to that explained for the catalyst C1, except that theslurry C was used instead of the slurry A. Hereinafter, this catalyst isreferred to as “catalyst C3”.

<Durability Test>

The catalysts C1 to C3 were subjected to a durability test in anelectric furnace. Specifically, the catalysts C1 to C3 were heated at750° C. for 5 hours in air.

<Evaluation of NO_(x) Adsorption Performance>

The catalysts C1 to C3 after the durability test were pre-treated byheating them to 400° C. Thereafter, these catalysts C1 to C3 were putinto a lean atmosphere for 2 minutes using a model gas apparatus. Then,the NO_(x) adsorption amounts during that time were measured. Themeasurements were carried out at 200° C. The results are shown in FIG.7.

FIG. 7 is a graph showing the results of the measurements of the NO_(x)adsorption amounts of the diesel exhaust gas purification catalysts.

As is apparent from FIG. 7, the catalysts C1 and C2 showed much moreexcellent NO_(x) adsorption performance as compared to that of thecatalyst C3. Specifically, the catalysts C1 and C2 had NO_(x) adsorptionamounts of 500 mg/L-NO₂ or more in NO₂ conversion. These adsorptionamounts are, for example, sufficient for adsorbing almost the wholeamount of NO_(x) that is emitted immediately after starting an engine.In addition, the catalyst C2 showed more excellent NO_(x) adsorptionperformance as compared to the catalyst C1.

<Evaluation of Performance for Purifying HC and CO>

A model gas comprising HC and CO was flown into the catalysts C1 to C3after the durability test while the temperature of these catalysts wasraised from room temperature to 400° C. Then, the total amount of HC orCO in the inflow gas and the total amount of HC or CO in the outflow gaswere obtained. Then, an HC and CO conversion was measured by calculatingthe difference of the total amount of HC or CO in the inflow gas and thetotal amount of HC or CO in the outflow gas over the total amount of HCor CO in the inflow gas. The result is shown in FIG. 8.

FIG. 8 is a graph showing the measurement result of the HC and COconversion of the diesel exhaust gas purification catalysts.

As is apparent from FIG. 8, the catalyst C2 showed a similar HC and COpurification performance to that of the catalyst C3. Furthermore,although the catalyst C1 had a slightly lower HC and CO conversion ascompared to that of the catalyst C3, it showed excellent HC and COpurification performance.

<Evaluation of NO_(x) Purification Performance>

Using each of the catalysts C1 to C3 after the durability test, thediesel exhaust gas purification system that has been explained withreference to FIG. 2 was prepared. Namely, systems each comprising eachof the catalysts C1 to C3 and a denitration catalyst to which theexhaust gas that has passed through each of the catalysts C1 to C3 issupplied were manufactured.

Thereafter, an NO conversion was measured for each of these systems. Asa result, the system using the catalyst C1 showed a higher NO_(x)conversion as compared to the system using the catalyst C3. Furthermore,the system using the catalyst C2 showed a much higher NO_(x) conversionas compared to the system using the catalyst C1.

From the results mentioned above, it was found that the catalysts C1 andC2 had more excellent functionality to improve the NO_(x) purificationperformance of the denitration catalyst as compared to the catalyst C3.Specifically, it was found that the catalyst C2 was further excellent inthis function as compared to the catalyst C1.

<<Effect of Composition of Composite Oxide>>

Example 4 Preparation of Catalyst C4

A composite oxide of cerium, lanthanum and praseodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. Furthermore, the ratio of lanthanum in this compositeoxide was adjusted to 5% by mass in terms of oxide. The specific surfacearea of the obtained composite oxide was 180 m²/g. Hereinafter, thiscomposite was referred to as “composite oxide Ox1”.

20 g of alumina, 120 g of the composite oxide Ox1, 135 g of zeolite, 100g of an alumina sol, 100 g of pure water, and a platinum nitratesolution containing 8 g of platinum, a palladium nitrate solutioncontaining 4 g of palladium, and a rhodium nitrate solution containing 2g of rhodium were mixed to prepare a slurry. Hereinafter, the slurry isreferred to as “slurry S1”.

A monolithic honeycomb carrier having a volume of 0.035 L was coatedwith the slurry S1. This was dried at 250° C. for 1 hour, and calcinedat 500° C. for 1 hour. A diesel exhaust gas purification catalyst wasprepared in this manner. Hereinafter, this catalyst is referred to as“catalyst C4”.

Example 5 Preparation of Catalyst C5

A composite oxide of cerium, lanthanum and praseodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. Furthermore, the ratio of lanthanum in this compositeoxide was adjusted to 5% by mass in terms of oxide. The specific surfacearea of the obtained composite oxide was 100 m²/g. Hereinafter, thiscomposite was referred to as “composite oxide Ox2”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox2 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C5”.

Example 6 Preparation of Catalyst C6

A composite oxide of cerium and zirconium was prepared. The ratio ofcerium in this composite oxide was adjusted to 80% by mass in terms ofoxide. The specific surface area of the obtained composite oxide was 80m²/g. Hereinafter, this composite was referred to as “composite oxideOx3”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox3 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C6”.

Example 7 Preparation of Catalyst C7

A composite oxide of cerium and praseodymium was prepared. The ratio ofcerium in this composite oxide was adjusted to 90% by mass in terms ofoxide. The specific surface area of the obtained composite oxide was 190m²/g. Hereinafter, this composite was referred to as “composite oxideOx4”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox4 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C7”.

Example 8 Preparation of Catalyst C8

A composite oxide of cerium and lanthanum was prepared. The ratio ofcerium in this composite oxide was adjusted to 90% by mass in terms ofoxide. The specific surface area of the obtained composite oxide was 165m²/g. Hereinafter, this composite was referred to as “composite oxideOx5”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox5 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C8”.

Example 9 Preparation of Catalyst C9

A composite oxide of cerium, zirconium, lanthanum, and praseodymium wasprepared. The ratio of cerium in this composite oxide was adjusted to80% by mass in terms of oxide. The ratio of zirconium in this compositeoxide was adjusted to 10% by mass in terms of oxide. Further, the ratioof lanthanum in this composite oxide was adjusted to 5% by mass in termsof oxide. The specific surface area of the obtained composite oxide was150 m²/g. Hereinafter, this composite was referred to as “compositeoxide Ox6”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox6 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C9”.

Example 10 Preparation of Catalyst C10

A composite oxide of cerium, praseodymium, and neodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. The ratio of praseodymium in this composite oxide wasadjusted to 5% by mass in terms of oxide. The specific surface area ofthe obtained composite oxide was 145 m²/g. Hereinafter, this compositewas referred to as “composite oxide Ox7”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox7 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C10”.

Example 11 Preparation of Catalyst C11

A composite oxide of cerium, praseodymium, and yttrium was prepared. Theratio of cerium in this composite oxide was adjusted to 90% by mass interms of oxide. The ratio of praseodymium in this composite oxide wasadjusted to 5% by mass in terms of oxide. The specific surface area ofthe obtained composite oxide was 130 m²/g. Hereinafter, this compositewas referred to as “composite oxide Ox8”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox8 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C11”.

Example 12 Preparation of Catalyst C12

A composite oxide of cerium and praseodymium was prepared. The specificsurface area of the obtained composite oxide was 180 m²/g. Hereinafter,this composite was referred to as “composite oxide Ox9”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 78 g of thecomposite oxide Ox9, 6 g of barium acetate (the weight in terms ofBaO₂), and 30 g of alumina were used instead of 120 g of the compositeoxide Ox1. Hereinafter, this catalyst is referred to as “catalyst C12”.

<Durability Test>

Each of the catalysts C4 to C12 was subjected to a similar durabilitytest to that mentioned previously for the catalysts C1 to C3.

<Evaluation of NO_(x) Adsorption Performance>

The NO_(x) adsorption performances of the catalysts C4 to C12 after thedurability test were evaluated by a similar method to that mentionedpreviously for the catalysts C1 to C3.

<Evaluation of Exhaust Gas Purification Performance>

The diesel exhaust gas purification systems that have been explainedwith reference to FIG. 2 were prepared by using each of the catalysts C4to C12 after the durability test. Namely, systems each comprising eachof the catalysts C4 to C12 and a denitration catalyst to which theexhaust gas that has passed through each of the catalysts C4 to C12 issupplied were manufactured. Thereafter, the conversions of CO, HC andNO_(x) at 200° C. were measured for each of these systems.

<Summary>

The above-mentioned evaluation results are summarized in the followingTable 1.

TABLE 1 Noble Metals Composite Oxides/Oxides Pt Pd Rh Ce Zr La Pr Nd YSSA Catalysts (g/L) (g/L) (g/L) (mass %) (mass %) (mass %) (mass %)(mass %) (mass %) Form (m²/g) C4 2 1 0.5 90 — 5 5 — — SS 180 C5 2 1 0.590 — 5 5 — — SS 100 C6 2 1 0.5 80 20 — — — — SS 80 C7 2 1 0.5 90 — — 10 — — SS 190 C8 2 1 0.5 90 — 10  — — — SS 165 C9 2 1 0.5 80 10 5 5 — — SS150 C10 2 1 0.5 90 — — 5 5 — SS 145 C11 2 1 0.5 90 — — 5 — 5 SS 130 C122 1 0.5 65 — — 5 — — SS 180 Composite Oxides/Oxides NO_(x) Theadsorption Whole amount Conversion Ba Al Content Zeolite (mg/L- (%)Catalysts (mass %) (mass %) (mass %) (mass %) Position NO₂) CO HC NO_(x)C4 — — 40 45 Upstream 600 75 80 80 C5 — — 40 45 Upstream 110 80 81 17 C6— — 40 45 Upstream 50 77 83 15 C7 — — 40 45 Upstream 535 74 78 73 C8 — —40 45 Upstream 360 76 83 55 C9 — — 40 45 Upstream 500 78 80 58 C10 — —40 45 Upstream 630 70 81 35 C11 — — 40 45 Upstream 450 71 79 50 C12  525 40 45 Upstream 700 68 75 90

Table 1 is a table in which the physical properties of the catalyst C4to C12 are summarized. In Table 1, in the respective columns of “NobleMetals”, the mass of the noble metal per unit volume of the substrate isdescribed. In Table 1, in the column of “Position”, the positionalrelationship between each catalyst and the denitration catalyst isdescribed. For example, the “Upstream” in this column means that eachcatalyst is disposed on the upstream side of the exhaust gas stream withrespect to the denitration catalyst. Furthermore, in Table 1, in thecolumn of “SSA”, the specific surface area of the composite oxideincluded in each catalyst is described. In addition, in Table 1, the“SS” means that the composite oxide forms a solid solution.

As is apparent from Table 1, when the composite oxide containing ceriumand praseodymium was used, particularly excellent NO_(x) adsorptionperformance and NO_(x) purification performance could be achieved.Furthermore, when the composite oxide having a specific surface area of130 m²/g or more was used, a specifically excellent NO_(x) adsorptionperformance and NO_(x) purification performance could be achieved. Inaddition, it was found that the NO_(x) adsorption performance and NO_(x)purification performance can be improved by further incorporatingbarium. This is assumed to be because barium has a function tochemically adsorb NO_(x).

<<Effect of Coating Composition>>

Example 13 Preparation of Catalyst C13

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 30 g of thecomposite oxide Ox1 was used instead of 120 g of the composite oxideOx1, and 225 g of zeolite was used instead of 200 g of zeolite.Hereinafter, this catalyst is referred to as “catalyst C13”.

Example 14 Preparation of Catalyst C14

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 105 g of thecomposite oxide Ox1 was used instead of 120 g of the composite oxideOx1, and 150 g of zeolite was used instead of 200 g of zeolite.Hereinafter, this catalyst is referred to as “catalyst C14”.

Example 15 Preparation of Catalyst C15

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 180 g of thecomposite oxide Ox1 was used instead of 120 g of the composite oxideOx1, and 75 g of zeolite was used instead of 200 g of zeolite.Hereinafter, this catalyst is referred to as “catalyst C15”.

Example 16 Preparation of Catalyst C16

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 225 g of thecomposite oxide Ox1 was used instead of 120 g of the composite oxideOx1, and the use of zeolite was omitted. Hereinafter, this catalyst isreferred to as “catalyst C16”.

<Durability Test>

Each of the catalysts C13 to C16 was subjected to a similar durabilitytest to that mentioned previously for the catalysts C1 to C3.

<Evaluation of NO_(x) Adsorption Performance>

The NO_(x) adsorption performances of the catalysts C13 to C16 after thedurability test were evaluated by a similar method to that mentionedpreviously for the catalysts C1 to C3.

<Evaluation of Exhaust Gas Purification Performance>

The diesel exhaust gas purification system that has been explained withreference to FIG. 2 was prepared by using each of the catalysts C13 toC16 after the durability test. Namely, systems each comprising each ofthe catalysts C13 to C16 and a denitration catalyst to which the exhaustgas that has passed through each of the catalysts C13 to C16 is suppliedwere manufactured. Thereafter, the conversions of CO, HC and NO_(x) at200° C. were measured for each of these systems in a similar manner tothat explained previously for the systems comprising the catalysts C4 toC12.

<Summary>

The above-mentioned evaluation results are summarized in the followingTable 2.

TABLE 2 NO_(x) adsorption Noble Metals Composite Oxides amountConversion Cata- Pt Pd Rh Ce La Pr SSA Content Zeolite (mg/L- (%) lysts(g/L) (g/L) (g/L) (mass %) (mass %) (mass %) Form (m²/g) (mass %) (mass%) Position NO₂) CO HC NO_(x) C13 2 1 0.5 90 5 5 SS 180 10 75 Upstream60 65 85 20 C14 2 1 0.5 90 5 5 SS 180 35 50 Upstream 300 70 85 60 C4 2 10.5 90 5 5 SS 180 40 45 Upstream 600 75 80 80 C15 2 1 0.5 90 5 5 SS 18060 25 Upstream 650 55 45 65 C16 2 1 0.5 90 5 5 SS 180 85 0 Upstream 67035 20 50

Table 2 is a table in which the physical properties of the catalysts C13to C16 and the catalyst C4 are summarized. The meanings of therespective descriptions in Table 2 are the same to those in Table 1.

As is apparent from Table 2, when the content of zeolite was increased,the HC purification performance was improved.

<<Effect of Constitution of Catalyst Layer>>

Example 17 Preparation of Catalyst C17

10 g of alumina, 90 g of the composite oxide Ox1, 67.5 g of zeolite, 50g of an alumina sol, 50 g of pure water, and a platinum nitrate solutioncontaining 4 g of platinum, a palladium nitrate solution containing 2 gof palladium, and a rhodium nitrate solution containing 1 g of rhodiumwere mixed to prepare a slurry. Hereinafter, the slurry is referred toas “slurry S2”.

A slurry was prepared in a similar manner to that for the slurry S2,except that 30 g of the composite oxide Ox1 was used instead of 90 g ofthe composite oxide Ox1. Hereinafter, the slurry is referred to as“slurry S3”.

A monolithic honeycomb carrier having a volume of 0.035 L was coatedwith the slurry A. This was dried at 250° C. for 1 hour, and calcined at500° C. for 1 hour. A first catalyst layer was thus formed on asubstrate.

Thereafter the first catalyst layer was coated with the slurry S3. Thiswas dried at 250° C. for 1 hour, and calcined at 500° C. for 1 hour. Asecond catalyst layer was thus formed on the first catalyst layer.

A diesel exhaust gas purification catalyst was prepared in the mannermentioned above. Hereinafter, this catalyst is referred to as “catalystC17”.

Example 18 Preparation of Catalyst C18 (Reference Example)

A slurry was prepared in a similar manner to that for the slurry S2,except that 60 g of the composite oxide Ox1 was used instead of 90 g ofthe composite oxide Ox1. Hereinafter, the slurry is referred to as“slurry S4”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that for the catalyst C17, except that the slurry S4 was usedinstead of the slurries S2 and S3. Hereinafter, this catalyst isreferred to as “catalyst C18”.

Example 19 Preparation of Catalyst C19

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that for the catalyst C17, except that the slurry S2 was usedinstead of the slurry S3, and the slurry S3 was used instead of theslurry S2. Hereinafter, this catalyst is referred to as “catalyst C19”.

Example 20 Preparation of Catalyst C20

A monolithic honeycomb carrier substrate having a volume of 0.035 L wascoated with the slurry S3 up to the position at 50% from the upstreamend of the substrate, and dried at 250° C. for 1 hour. The substrate wasthen coated with the slurry S2 up to the position at 50% from thedownstream end of the substrate, and dried at 250° C. for 1 hour. Theobtained was then calcined at 500° C. for 1 hour. A diesel exhaust gaspurification catalyst was manufactured in this manner. Hereinafter, thiscatalyst is referred to as “catalyst C20”.

Example 21 Preparation of Catalyst C21 (Reference Example)

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that for the catalyst C20, except that the slurry S4 was usedinstead of the slurries S2 and S3. Hereinafter, this catalyst isreferred to as “catalyst C21”.

Example 22 Preparation of Catalyst C22

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that for the catalyst C20, except that the slurry S2 was usedinstead of the slurry S3, and the slurry S3 was used instead of theslurry S2. Hereinafter, this catalyst is referred to as “catalyst C22”.

<Durability Test>

Each of the catalysts C17 to C22 was subjected to a similar durabilitytest to that mentioned previously for the catalysts C1 to C3.

<Evaluation of NO_(x) Adsorption Performance>

The NO_(x) adsorption performances of the catalysts C17 to C22 after thedurability test were evaluated by a similar method to that mentionedpreviously for the catalysts C1 to C3.

<Evaluation of Exhaust Gas Purification Performance>

The diesel exhaust gas purification system that has been explained withreference to FIG. 2 was prepared by using each of the catalysts C17 toC22 after the durability test. Namely, systems each comprising each ofthe catalysts C17 to C22 and a denitration catalyst to which the exhaustgas that has passed through each of the catalysts C17 to C22 is suppliedwere manufactured. Thereafter, the conversions of CO, HC and NO_(x) at200° C. were measured for each of these systems in a similar manner tothat explained previously for the systems comprising the catalysts C4 toC12.

<Summary>

The above-mentioned evaluation results are summarized in the followingTables 3 and 4.

TABLE 3 Noble Metals Composite Oxide Pt Pd Rh Ce La Pr SSA CatalystsLayers (g/L) (g/L) (g/L) (mass %) (mass %) (mass %) Form (m²/g) C17Second Catalyst Layer 1 0.5 0.25 90 5 5 SS 180 First Catalyst Layer 10.5 0.25 90 5 5 SS 180 C18 Second Catalyst Layer 1 0.5 0.25 90 5 5 SS180 First Catalyst Layer 1 0.5 0.25 90 5 5 SS 180 C19 Second CatalystLayer 1 0.5 0.25 90 5 5 SS 180 First Catalyst Layer 1 0.5 0.25 90 5 5 SS180 NO_(x) Composite adsorption Oxide amount Conversion Content Zeolite(mg/L- (%) Catalysts Layers (mass %) (mass %) Position NO₂) CO HC NO_(x)C17 Second Catalyst Layer 30 22.5 Upstream 630 75 70 85 First CatalystLayer 10 22.5 C18 Second Catalyst Layer 20 22.5 Upstream 600 75 80 80First Catalyst Layer 20 22.5 C19 Second Catalyst Layer 10 22.5 Upstream430 75 80 50 First Catalyst Layer 30 22.5

TABLE 4 Noble Metals Composite Oxide Pt Pd Rh Ce La Pr SSA CatalystsParts (g/L) (g/L) (g/L) (mass %) (mass %) (mass %) Form (m²/g) C20 FirstPart 1 0.5 0.25 90 5 5 SS 180 Second Part 1 0.5 0.25 90 5 5 SS 180 C21First Part 1 0.5 0.25 90 5 5 SS 180 Second Part 1 0.5 0.25 90 5 5 SS 180C22 First Part 1 0.5 0.25 90 5 5 SS 180 Second Part 1 0.5 0.25 90 5 5 SS180 NO_(x) Composite adsorption Oxide amount Conversion Content Zeolite(mg/L- (%) Catalysts Parts (mass %) (mass %) Position NO₂) CO HC NO_(x)C20 First Part 30 22.5 Upstream 650 70 75 60 Second Part 10 22.5 C21First Part 20 22.5 Upstream 610 70 75 80 Second Part 20 22.5 C22 FirstPart 10 22.5 Upstream 550 75 81 92 Second Part 30 22.5

Table 3 is a table in which the physical properties of the catalyst C17to C19 are summarized. Table 4 is a table in which the physicalproperties of the catalyst C20 to C22 are summarized. The meanings ofthe respective descriptions in Tables 3 and 4 are similar to those inTable 1.

As is apparent from Table 3, the NO_(x) adsorption performance andNO_(x) purification performance could be improved by increasing thecomposite oxide content in the second catalyst layer.

As is apparent from Table 4, the NO_(x) adsorption performance andNO_(x) purification performance could be improved by increasing thecomposite oxide content in the second part.

<<Effect of Specific Surface Area of Composite Oxide>>

Example 23 Preparation of Catalyst C23

A composite oxide of cerium, lanthanum, and praseodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. The ratio of lanthanum in this composite oxide wasadjusted to 5% by mass in terms of oxide. The specific surface area ofthe obtained composite oxide was 120 m²/g. Hereinafter, this compositewas referred to as “composite oxide Ox10”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox10 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C23”.

Example 24 Preparation of Catalyst C24

A composite oxide of cerium, lanthanum, and praseodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. The ratio of lanthanum in this composite oxide wasadjusted to 5% by mass in terms of oxide. The specific surface area ofthe obtained composite oxide was 150 m²/g. Hereinafter, this compositewas referred to as “composite oxide Ox11”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox11 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C24”.

Example 25 Preparation of Catalyst C25

A composite oxide of cerium, lanthanum, and praseodymium was prepared.The ratio of cerium in this composite oxide was adjusted to 90% by massin terms of oxide. The ratio of lanthanum in this composite oxide wasadjusted to 5% by mass in terms of oxide. The specific surface area ofthe obtained composite oxide was 210 m²/g. Hereinafter, this compositewas referred to as “composite oxide Ox12”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox12 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C25”.

<Durability Test>

Each of the catalysts C23 to C25 was subjected to a similar durabilitytest to that mentioned previously for the catalysts C1 to C3.

<Evaluation of NO_(x) Adsorption Performance>

The NO_(x) adsorption performances of the catalysts C23 to C25 after thedurability test were evaluated by a similar method to that mentionedpreviously for the catalysts C1 to C3.

<Evaluation of Exhaust Gas Purification Performance>

The diesel exhaust gas purification system that has been explained withreference to FIG. 2 was prepared by using each of the catalysts C23 toC25 after the durability test. Namely, systems each comprising each ofthe catalysts C23 to C25 and a denitration catalyst to which the exhaustgas that has passed through each of the catalysts C23 to C25 is suppliedwere manufactured. Thereafter, the conversions of CO, HC and NO_(x) at200° C. were measured for each of these systems in a similar manner tothat explained previously for the systems comprising the catalysts C4 toC12.

<Summary>

The above-mentioned evaluation results are summarized in the followingTable 5.

TABLE 5 NO_(x) adsorption Noble Metals Composite Oxides amountConversion Cata- Pt Pd Rh Ce La Pr SSA Content Zeolite (mg/L- (%) lysts(g/L) (g/L) (g/L) (mass %) (mass %) (mass %) Form (m²/g) (mass %) (mass%) Position NO₂) CO HC NO_(x) C23 2 1 0.5 90 5 5 SS 120 40 45 Upstream142 65 78 20 C24 2 1 0.5 90 5 5 SS 150 40 45 Upstream 460 70 80 53 C4 21 0.5 90 5 5 SS 180 40 45 Upstream 600 75 80 80 C25 2 1 0.5 90 5 5 SS210 40 45 Upstream 715 75 81 92

Table 5 is a table in which the physical properties of the catalysts C23to C25 and the catalyst C4 are summarized. The meanings of therespective descriptions in Table 5 are similar to those in Table 1.

As is apparent from Table 5, the NO_(x) adsorption performance andexhaust gas purification performance were improved by increasing thespecific surface area of the composite oxide.

Other Comparative Examples Example 26 Preparation of Catalyst C26(Comparative Example)

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that the use ofnoble metals was omitted. Hereinafter, this catalyst is referred to as“catalyst C26”.

Example 27 Preparation of Catalyst C27 (Comparative Example)

Alumina having a specific surface area of 180 m²/g was prepared.Hereinafter, this alumina is referred to as “alumina A1”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thealumina A1 was used instead of 120 g of the composite oxide Ox1.Hereinafter, this catalyst is referred to as “catalyst C27”.

Example 28 Preparation of Catalyst C28 (Comparative Example)

A composite oxide of cerium and aluminum was prepared. The ratio ofcerium in this composite oxide was adjusted to 90% by mass in terms ofoxide. The specific surface area of the obtained composite oxide was 180m²/g. Hereinafter, this composite was referred to as “composite oxideOx13.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of thecomposite oxide Ox13 was used instead of 120 g of the composite oxideOx1. Hereinafter, this catalyst is referred to as “catalyst C28”.

Example 29 Preparation of Catalyst C29 (Comparative Example)

A diesel exhaust gas purification catalyst having a similar constitutionto that of the catalyst C4 was prepared in a similar manner to thatexplained previously. Hereinafter, this catalyst is referred to as“catalyst 29”. As mentioned below, the catalyst C29 was used bydisposing it on the downstream side of the denitration catalyst.

Example 30 Preparation of Catalyst C30 (Comparative Example)

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that a mixture of108 g of cerium oxide and 6 g of lanthanum oxide and 6 g of praseodymiumoxide was used instead of 120 g of the composite oxide Ox1. Hereinafter,this catalyst is referred to as “catalyst C30”.

Example 31 Preparation of Catalyst C31 (Comparative Example)

Cerium oxide having a specific surface area of 150 m²/g was prepared.Hereinafter, this cerium oxide is referred to as “ceria C1”.

A diesel exhaust gas purification catalyst was prepared in a similarmanner to that explained for the catalyst C4, except that 120 g of theceria C1 was used instead of 120 g of the composite oxide Ox1.Hereinafter, this catalyst is referred to as “catalyst C31”.

<Durability Test>

Each of the catalysts C26 to C31 was subjected to a similar durabilitytest to that mentioned previously for the catalysts C1 to C3.

<Evaluation of NO_(x) Adsorption Performance>

The NO_(x) adsorption performances of the catalysts C26 to C31 after thedurability test were evaluated by a similar method to that mentionedpreviously for the catalysts C1 to C3.

<Evaluation of Exhaust Gas Purification Performance>

The diesel exhaust gas purification system that has been explained withreference to FIG. 2 was prepared by using each of the catalysts C26 toC28 and C30 and C31 after the durability test. Namely, systems eachcomprising each of the catalysts C26 to C28 and C30 and C31 and adenitration catalyst to which the exhaust gas that has passed througheach of the catalysts C26 to C28 and C30 and C31 is supplied wereprepared. Furthermore, for comparison, a system comprising a denitrationcatalyst and the catalyst 29 to which the exhaust gas that has passedthrough the denitration catalyst is supplied was prepared. Thereafter,the conversions of CO, HC and NO_(x) at 200° C. were measured for eachof these systems in a similar manner to that explained previously forthe systems comprising the catalysts C4 to C12.

<Summary>

The above-mentioned evaluation results are summarized in the followingTable 6.

TABLE 6 Noble Metals Composite Oxides/Cerium Oxides Pt Pd Rh Ce La Pr AlSSA Content Catalysts (g/L) (g/L) (g/L) (mass %) (mass %) (mass %) (mass%) Form (m²/g) (mass %) C26 — — — 90 5 5 — SS 180 40 C27 2 1 0.5 — — — —— — — C28 2 1 0.5 90 — — 10 SS 180 40 C29 2 1 0.5 90 5 5 — SS 180 40 C302 1 0.5 90 5 5 — MIX 180 40 C31 2 1 0.5 100  — — — — 150 40 NO_(x)adsorption amount Conversion Zeolite (mg/L- (%) Catalysts (mass %)Position NO₂) CO HC NO_(x) C26 45 Upstream 30 0 20 5 C27 45 Upstream 4070 80 10 C28 45 Upstream 330 75 80 35 C29 45 Downstream 600 65 68 40 C3045 Upstream 285 70 80 33 C31 45 Upstream 350 68 77 38

Table 6 is a table in which the physical properties of the catalysts C26to C31 and the catalyst C4 are summarized. In Table 6, the “MIX” meansthat a mixture of a plurality of oxides was used. The meanings of otherdescriptions in Table 6 are similar to those in Table 1.

As is apparent from Table 6, when the noble metal was omitted, theNO_(x) adsorption amount and exhaust gas purification performance werelow. When cerium was omitted, the NO_(x) adsorption amount andperformances for purifying CO and NO_(x) were low. When the compositeoxide of cerium and an element other than Group III and/or Group IV wasused, the NO_(x) adsorption amount and performance for purifying NO_(x)were low. When the catalyst was disposed on the downstream side of thedenitration catalyst, the exhaust gas purification performance was low.When the mixture of a plurality of oxides was used instead of thecomposite oxide, the NO_(x) adsorption amount and performance forpurifying NO_(x) were low. In addition, when the single oxide of ceriumwas used instead of the composite oxide, the NO_(x) adsorption amountand exhaust gas purification performance were low.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventiveconcept as defined by the appended claims and their equivalents.

What is claimed is:
 1. A diesel exhaust gas purification catalyst,comprising: a substrate; a catalyst layer formed on the substrate, thecatalyst layer comprising a carrier, a noble metal and/or an oxidethereof supported by the carrier, and a composite oxide of cerium andone or more Group III and/or Group IV elements; and a first partcontaining the composite oxide of cerium and one or more Group IIIand/or Group IV elements to which exhaust gas is fed and a second partcontaining the composite oxide of cerium and one or more Group IIIand/or Group IV elements to which the exhaust gas that has passedthrough the first part is fed, the first part consisting of a smallercontent of the composite oxide of cerium and one or more Group IIIand/or Group IV elements per unit volume than that of the second part,wherein the catalyst when in use is disposed on an upstream side of anexhaust gas stream with respect to a denitration catalyst.
 2. The dieselexhaust gas purification catalyst according to claim 1, the catalystlayer comprising: a first catalyst layer formed on the substrate; and asecond catalyst layer formed on the first layer, the second catalystlayer comprising a larger content of the composite oxide per unit volumethan that of the first catalyst layer.
 3. The diesel exhaust gaspurification catalyst according to claim 1, wherein the composite oxidecomprises the Group III element, and the Group III element is alanthanoid and/or an actinoid.
 4. the diesel exhaust gas purificationcatalyst according to claim 1, wherein the composite oxide comprises theGroup III element, and the Group III element is lanthanum and/orpraseodymium.
 5. The diesel exhaust gas purification catalyst accordingto claim 1, wherein the ratio of the cerium in the composite oxide is inthe range of from 55% to 95% by mass in terms of oxides.
 6. The dieselexhaust gas purification catalyst according to claim 1, wherein thecomposite oxide has a specific surface area of 150 m²/g or more.
 7. Thediesel exhaust gas purification catalyst according to claim 1, whereinthe catalyst layer further comprises zeolite.
 8. A diesel exhaust gaspurification system, comprising: the diesel exhaust gas purificationcatalyst according to claim 1; and a denitration catalyst to whichexhaust gas that has passed through the diesel exhaust gas purificationcatalyst is fed.
 9. A diesel exhaust gas purification system,comprising: a diesel oxidizing catalyst; the diesel exhaust gaspurification catalyst according to claim 1 to which exhaust gas that haspassed through the diesel oxidizing catalyst is fed; and a denitrationcatalyst to which the exhaust gas that has passed through the dieselexhaust gas purification catalyst is fed.
 10. The diesel exhaust gaspurification system according to claim 9, further comprising a dieselparticulate filter between the diesel oxidizing catalyst and the dieselexhaust gas purification catalyst.
 11. The diesel exhaust gaspurification catalyst according to claim 1, wherein the composite oxidecontent in the first part per unit volume is 10 mass % or more.